U.S. patent number 8,058,219 [Application Number 12/090,213] was granted by the patent office on 2011-11-15 for metals compatible post-etch photoresist remover and/or sacrificial antireflective coating etchant.
This patent grant is currently assigned to Advanced Technology Materials, Inc.. Invention is credited to Thomas H. Baum, David D. Bernhard, Ping Jiang, Michael B. Korzenski, Melissa K. Rath, Renjie Zhou.
United States Patent |
8,058,219 |
Rath , et al. |
November 15, 2011 |
Metals compatible post-etch photoresist remover and/or sacrificial
antireflective coating etchant
Abstract
A liquid removal composition and process for removing
photoresist and/or sacrificial anti-reflective coating (SARC)
material from a microelectronic device having same thereon. The
liquid removal composition includes at least one organic quaternary
base and at least one surface interaction enhancing additive. The
composition achieves at least partial removal of photoresist and/or
SARC material in the manufacture of integrated circuitry with
minimal etching of metal species on the microelectronic device,
such as copper and cobalt, and without damage to low-k dielectric
materials employed in the microelectronic device architecture.
Inventors: |
Rath; Melissa K. (Danbury,
CT), Bernhard; David D. (Kooskia, ID), Baum; Thomas
H. (New Fairfield, CT), Jiang; Ping (Danbury, CT),
Zhou; Renjie (Dayton, NJ), Korzenski; Michael B.
(Danbury, CT) |
Assignee: |
Advanced Technology Materials,
Inc. (Danbury, CT)
|
Family
ID: |
37963086 |
Appl.
No.: |
12/090,213 |
Filed: |
October 12, 2006 |
PCT
Filed: |
October 12, 2006 |
PCT No.: |
PCT/US2006/039888 |
371(c)(1),(2),(4) Date: |
October 06, 2008 |
PCT
Pub. No.: |
WO2007/047365 |
PCT
Pub. Date: |
April 26, 2007 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20090118153 A1 |
May 7, 2009 |
|
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
60726410 |
Oct 13, 2005 |
|
|
|
|
Current U.S.
Class: |
510/175; 510/176;
134/1.3 |
Current CPC
Class: |
C11D
3/43 (20130101); H01L 21/02063 (20130101); H01L
21/3212 (20130101); C11D 7/32 (20130101); C11D
3/3773 (20130101); C11D 3/26 (20130101); G03F
7/425 (20130101); C11D 11/0047 (20130101); C09D
9/04 (20130101); C23G 1/20 (20130101); C11D
3/30 (20130101); C11D 7/3209 (20130101); G03F
7/426 (20130101) |
Current International
Class: |
C11D
3/39 (20060101) |
Field of
Search: |
;510/175,176,220,226,376
;134/1.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1128221 |
|
Aug 2001 |
|
EP |
|
0213242 |
|
Feb 2002 |
|
WO |
|
2004059700 |
|
Jul 2004 |
|
WO |
|
2006074316 |
|
Jul 2006 |
|
WO |
|
Other References
European Patent Office, Supplemental European Search Report, Dec.
5, 2008. cited by other.
|
Primary Examiner: Webb; Gregory
Attorney, Agent or Firm: Fuierer; Tristan A. Moore & Van
Allen PLLC Yaghmour; Rosa
Claims
The invention claimed is:
1. A liquid removal composition comprising at least one organic
quaternary base, at least one surface interaction enhancing
additive, and optionally at least one component selected from the
group consisting of: at least one alkali or alkaline earth metal
source; at least one organic solvent; at least one surfactant; at
least one chelating agent; and combinations thereof, wherein said
at least one surface interaction enhancing additive comprises a
species selected from the group consisting of
poly(acrylamide-co-diallyldimethylammonium chloride),
poly(acrylamide), poly(diallyldimethylammonium chloride),
diallyldimethylammonium chloride, acrylamide, acetoguanamine, and
combinations thereof, and wherein said liquid removal composition
is useful for removing photoresist and/or sacrificial
anti-reflective coating (SARC) materials from a microelectronic
device having such material(s) thereon.
2. The liquid removal composition of claim 1, wherein the at least
one organic quaternary base comprises a compound having the formula
NR.sup.1R.sup.2R.sup.3R.sup.4OH, wherein R.sup.1, R.sup.2, R.sup.3
and R.sup.4 may be the same as or different from one another and
are selected from the group consisting of hydrogen,
straight-chained C.sub.1-C.sub.6 alkyl, branched C.sub.1-C.sub.6
alkyl, substituted C.sub.6-C.sub.10 aryl, and unsubstituted
C.sub.6-C.sub.10 aryl, alcohol groups, alkenes, and alkynes.
3. The liquid removal composition of claim 1, wherein the at least
one quaternary organic base comprises a compound selected from the
group consisting of tetrabutylammonium hydroxide,
benzyltrimethylammonium hydroxide (BTMAH), tetramethylammonium
hydroxide (TMAH), and combinations thereof.
4. The liquid removal composition of claim 1, comprising the alkali
or alkaline earth metal source, wherein the at least one alkali or
alkaline earth metal source comprises a potassium salt selected
from the group consisting of potassium hydroxide, potassium
chloride, and combinations thereof.
5. The liquid removal composition of claim 1, comprising the
organic solvent, wherein the at least one organic solvent comprises
a component selected from the group consisting of an amine, a
sulfur-containing compound, a glycol, a glycol ether, and
combinations thereof.
6. The liquid removal composition of claim 5, wherein the organic
solvent comprises a compound selected from the group consisting of
monoethanolamine, triethanolamine, triethylenediamine,
methylethanolamine, methyldiethanolamine,
pentamethyldiethylenetriamine, dimethyldiglycolamine,
1,8-diazabicyclo[5.4.0]undecene, aminopropylmorpholine,
hydroxyethylmorpholine, aminoethylmorpholine,
hydroxypropylmorpholine, diglycolamine, N-methylpyrrolidinone
(NMP), N-octylpyrrolidinone, N-phenylpyrrolidinone,
cyclohexylpyrrolidinone, vinyl pyrrolidinone, tetramethyl sulfone,
ethylene glycol, propylene glycol, neopentyl glycol, diethylene
glycol monomethyl ether, triethylene glycol monomethyl ether,
diethylene glycol monoethyl ether, triethylene glycol monoethyl
ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl
ether, diethylene glycol monobutyl ether, triethylene glycol
monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol
monohexyl ether, ethylene glycol phenyl ether, propylene glycol
methyl ether, dipropylene glycol methyl ether, tripropylene glycol
methyl ether, propylene glycol n-propyl ether, dipropylene glycol
n-propyl ether, tripropylene glycol n-propyl ether, propylene
glycol n-butyl ether, dipropylene glycol n-butyl ether,
tripropylene glycol n-butyl ether, propylene glycol phenyl ether,
and combinations thereof.
7. The liquid removal composition of claim 1, comprising the
chelating agent, wherein the at least one chelating agent comprises
a species selected from the group consisting of benzotriazole,
tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole,
3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole,
hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole,
1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole,
3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole,
3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole,
halo-benzotriazoles, naphthotriazole, 2-mercaptobenzoimidizole,
2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole,
2-mercaptothiazoline, 5-aminotetrazole,
5-amino-1,3,4-thiadiazole-2-thiol,
2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine,
methyltetrazole, 1,3-dimethyl-2-imidazolidinone,
1,5-mentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,
diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione,
mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino
-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate,
indiazole, guanine, urea, adenine, glycerol, thioglycerol,
nitrilotriacetic acid, salicylamide, benzoguanamine, melamine,
thiocyranuric acid, anthranilic acid, gallic acid, ascorbic acid,
salicylic acid, 8-hydroxyquinoline, 5-carboxylic
acid-benzotriazole, 3-mercaptopropanol, boric acid, and
iminodiacetic acid.
8. The liquid removal composition of claim 1, comprising the
surfactant, wherein said at least one surfactant comprises a
species selected from the group consisting of bis-(2-hydroxyethyl)
isodecyloxypropylamine oxide, alkoxylated ether amine oxides, ether
amine oxides derived from a branched chain C.sub.10 alcohol, and
combinations thereof.
9. The liquid removal composition of claim 1, further comprising
photoresist and/or SARC residue material, wherein said photoresist
and/or SARC residue material comprises a species selected from the
group consisting of: organic photoresist residue; ion-implanted
elements selected from the group consisting of boron, arsenic and
phosphorus; silicon-containing residue; and plasma-etching gas
elements selected from the group consisting of oxygen and
fluorine.
10. The liquid removal composition of claim 1, wherein the pH is in
a range from about 11 to about 14.
11. The liquid removal composition of claim 1, comprising
benzyltrimethylammonium hydroxide and
poly(acrylamide-co-diallyldimethylammonium chloride).
12. The liquid removal composition of claim 11, further comprising
sulfolane, di(ethylene glycol) methyl ether, KOH, propylene glycol,
MBI, and water.
13. A kit comprising, in one or more containers, one or more of the
following reagents for forming a liquid removal composition, said
one or more reagents selected from the group consisting of at least
one organic quaternary base, at least one surface interaction
enhancing additive, and optionally at least one component selected
from the group consisting of: at least one alkali or alkaline earth
metal source; at least one organic solvent; at least one
surfactant; at least one chelating agent; and combinations thereof,
and wherein the kit is adapted to form the composition of claim
1.
14. A method of removing photoresist and/or SARC material from a
microelectronic device having said material thereon, said method
comprising contacting the microelectronic device with a liquid
removal composition for sufficient time to at least partially
remove said material from the microelectronic device, wherein the
liquid removal composition comprises at least one organic
quaternary base, at least one surface interaction enhancing
additive, and optionally at least one component selected from the
group consisting of: at least one alkali or alkaline earth metal
source; at least one organic solvent; at least one surfactant; at
least one chelating agent; and combinations thereof, wherein said
at least one surface interaction enhancing additive comprises a
species selected from the group consisting of
poly(acrylamide-co-diallyldimethylammonium chloride),
poly(acrylamide), poly(diallyldimethylammonium chloride),
diallyldimethylammonium chloride, acrylamide, acetoguanamine, and
combinations thereof.
15. The method of claim 14, wherein the material comprises a layer
selected from the group consisting of: photoresist hardened by
plasma etching, photoresist hardened by ion implantation, and SARC
materials.
16. The method of claim 14, wherein said contacting is carried out
at conditions selected from the group consisting of: time of from
about 1 minute to about 60 minutes; temperature in a range of from
about 30.degree. C. to about 80.degree. C.; and combinations
thereof
17. The method of claim 14, further comprising rinsing the
microelectronic device with deionized water following contact with
the liquid removal composition.
18. A liquid removal composition comprising at least one quaternary
base, potassium chloride, and at least one chelator/passivating
agent, wherein the chelator/passivating agent comprises a species
selected from the group consisting of urea,
2-mercaptobenzimidazole, and combinations thereof.
19. The removal composition of claim 18, wherein the
chelator/passivating agent comprises urea.
20. A method of removing photoresist and/or SARC material from a
microelectronic device having said material thereon, said method
comprising contacting the microelectronic device with the liquid
removal composition of claim 18 for sufficient time to at least
partially remove said material from the microelectronic device.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is filed under the provisions of 35 U.S.C.
.sctn.371 and claims the priority of International Patent
Application No. PCT/US2006/039888 filed on 12 Oct. 2006, which
claims priority to U.S. Provisional Patent Application No.
60/726,410 filed on 13 Oct. 2005, which are both hereby
incorporated herein in their entireties.
FIELD OF THE INVENTION
The present invention relates to liquid removal compositions and
processes useful in microelectronic device manufacturing processes,
particularly for photoresist removal and silicate stripping, e.g.,
liquid removal of sacrificial anti-reflective silicate material,
from a microelectronic device having such material deposited
thereon, particularly where the sacrificial anti-reflective
silicate material is present with permanent silicate materials and
interconnect metals desired to be unaffected by the liquid removal
composition.
DESCRIPTION OF THE RELATED ART
Currently, there are four developed wavelengths of radiation used
in the photolithographic industry--436 nm, 365 nm, 248 nm, and 193
nm--and recent efforts have focused on 157 nm lithography
processes. In theory, with each wavelength decrease, smaller
features can be created on the microelectronic device chip.
However, because the reflectivity of the microelectronic device
substrate is inversely proportional to the photolithographic
wavelength, interference and unevenly exposed photoresist have
limited the consistency of the critical dimensions of the
microelectronic device.
For example, upon exposure to DUV radiation, it is well known that
the transmissivity of photoresist combined with the high
reflectivity of the substrates to the DUV wavelengths results in
the reflection of the DUV radiation back into the photoresist
thereby producing standing waves in the photoresist layer. The
standing waves trigger further photochemical reactions in the
photoresist causing an uneven exposure of the photoresist,
including in the masked portions not intended to be exposed to the
radiation, which results in variations in linewidths, spacing and
other critical dimensions.
In order to address the transmissivity and reflectivity problems,
bi- and tri-layer photoresists, bottom anti-reflective coatings
(BARCs), and sacrificial anti-reflective coatings (SARCs) have been
developed which are applied to substrates prior to applying the
photoresist. All of these antireflective coatings have a
planarizing effect on topological wafer surfaces encountered in
typical dual damascene integration and all incorporate a UV
chromophore into a spin-on polymer matrix which will absorb
incident UV radiation.
When used with SiOC-based dielectrics, SARCs have two important
advantages: SARCs are TEOS-based and thus etch at the same rate as
SiOC dielectrics, which allows for much greater etch uniformity and
control such that the trench etch stop can be eliminated and via
etch stop can be reduced in thickness by up to 50%; and etched
SARCs can be removed using liquid removal compositions because
there is not a significant increase in post-etch cross-linking in
etched SARCs relative to etched photoresist and etched BARCs.
Untreated photoresist possesses solubility in strong aqueous
alkaline solutions as well as solutions of select organic solvents.
However, photoresist that has been exposed to gas-phase plasma
etching, such as is typically used for etching of dielectric
materials, will develop a hardened crust on the surface of the
material. The hardened crust is composed of cross-linked organic
polymer and may contain small amounts of silicon or metal atoms.
Fluorine-based plasma etches as used in dual damascene processes
may deposit fluorine atoms in the photoresist crust, which may
decrease its solubility and increase its resistance to chemical
removal.
The clean removal of hardened photoresist and/or SARC materials
from the microelectronic device wafer has proven to be difficult
and/or costly. If not removed, the layers may interfere with
subsequent silicidation or contact formation. Typically, the layers
are removed by oxidative or reductive plasma ashing or wet
cleaning. However, plasma ashing, whereby the substrate is exposed
to an oxidative or reductive plasma etch, may result in damage to
the dielectric material, either by changing the feature shapes and
dimensions, or by an increase in the dielectric constant of the
dielectric material. The latter problem is more pronounced when
low-k dielectric materials, such as organosilicate glasses (OSG) or
carbon-doped oxide glasses, are the underlying dielectric material.
As such, it is often desirable to avoid the use of plasma ashing to
remove the hardened photoresist and/or SARC layers.
When a cleaner/etchant composition is used in back-end-of-line
(BEOL) applications to process aluminum, copper or cobalt
interconnected wires, it is important that the composition possess
good metal compatibility, e.g., a low etch rate on copper,
aluminum, cobalt, etc., and that the permanent silicate materials
be unaffected by the cleaner composition. Aqueous removal solutions
are preferred because of the simpler disposal techniques, however,
the photoresist "crust" is typically extremely insoluble in aqueous
cleaners, especially cleaners that do not damage the dielectric.
Moreover, aqueous removal solutions are known to etch the metal
interconnects.
Hydrogen fluoride (HF) solutions may be used to etch silicon oxide
materials. However, HF solutions etch silicon oxides rapidly and
non-selectively, and thereby may cause damage or loss of other
silicate-containing materials in the device, especially silicate
materials that are commonly used as ILDs. Such ILD materials
include, by way of example, silicon dioxide, fluorinated silicate
glass (FSG), and organosilicate glass (OSG), including both porous
and non-porous materials.
Accordingly, there is a need in the art for HF-free liquid removal
compositions that can completely and efficiently remove photoresist
and/or SARC layers from the microelectronic device while
simultaneously minimizing damage to the co-extensively present
dielectric materials and/or interconnect metals.
SUMMARY OF THE INVENTION
The present invention relates to a liquid removal composition and
process useful in microelectronic device manufacturing processes,
particularly for the removal of sacrificial anti-reflective
silicate material and photoresist material from a microelectronic
device having such material deposited thereon, particularly where
the sacrificial anti-reflective silicate material is present with
permanent silicate materials and interconnect metals desired to be
unaffected by said composition.
One aspect of the invention relates to substrate treatment
formulations such as cleaning formulations comprising surface
interaction enhancing agents including, but not limited to,
poly(acrylamide-co-diallyldiemethylammonium chloride),
poly(acrylamide), poly(acrylic acid), poly(diallyldiemethylammonium
chloride), diallyldimethylammonium chloride, acrylamide,
acetoguanamine, and combinations thereof. Preferably, the treatment
formulation comprises less than 50 wt % water, more preferably less
than 40 wt % water, even more preferably less than 30 wt % water
and even more preferably less than 25 wt % water.
In another aspect, the present invention relates to a liquid
removal composition comprising at least one organic quaternary
base, at least one surface interaction enhancing additive, and
optionally at least one component selected from the group
consisting of: at least one alkali or alkaline earth metal source;
at least one organic solvent; at least one surfactant; at least one
chelating agent; and combinations thereof, wherein said liquid
removal composition is useful for removing photoresist and/or
sacrificial anti-reflective coating (SARC) materials from a
microelectronic device having such material(s) thereon. Preferably,
the liquid removal composition is devoid of abrasive materials and
is not supercritical or subcritical.
In still another aspect, the present invention relates to a liquid
removal composition comprising at least one organic quaternary
base, at least one alkali or alkaline earth metal source, at least
one organic solvent, at least one surface interaction enhancing
additive, optionally at least one surfactant, and optionally at
least one chelating agent, wherein said liquid removal composition
is useful for removing photoresist and/or sacrificial
anti-reflective coating (SARC) materials from a microelectronic
device having such material(s) thereon.
In yet another aspect, the present invention relates to a kit
comprising, in one or more containers, one or more of the following
reagents for forming a liquid removal composition, said one or more
reagents selected from the group consisting of at least one organic
quaternary base, at least one surface interaction enhancing
additive, and optionally at least one component selected from the
group consisting of: at least one alkali or alkaline earth metal
source; at least one organic solvent; at least one surfactant; at
least one chelating agent; and combinations thereof, and wherein
the kit is adapted to form the liquid removal composition suitable
for removing photoresist and/or SARC materials from a
microelectronic device having said material(s) thereon.
In still another aspect, the present invention relates to a method
of removing material from a microelectronic device having said
material thereon, said method comprising contacting the
microelectronic device with a liquid removal composition for
sufficient time to at least partially remove said material from the
microelectronic device, wherein the liquid removal composition
comprises at least one organic quaternary base, at least one
surface interaction enhancing additive, and optionally at least one
component selected from the group consisting of: at least one
alkali or alkaline earth metal source; at least one organic
solvent; at least one surfactant; at least one chelating agent; and
combinations thereof.
In yet another aspect, the present invention relates to a method of
removing photoresist and/or SARC material from a microelectronic
device having said material thereon, said method comprising
contacting the microelectronic device with a liquid removal
composition for sufficient time to at least partially remove said
material from the microelectronic device, wherein the liquid
removal composition comprises at least one organic quaternary base,
at least one surface interaction enhancing additive, and optionally
at least one component selected from the group consisting of: at
least one alkali or alkaline earth metal source; at least one
organic solvent; at least one surfactant; at least one chelating
agent; and combinations thereof.
In a further aspect, the present invention relates to a method of
removing photoresist and/or SARC material from a microelectronic
device having said material thereon, said method comprising
contacting the microelectronic device with a liquid removal
composition for sufficient time to at least partially remove said
material from the microelectronic device, wherein the liquid
removal composition comprises at least one organic quaternary base,
at least one alkali or alkaline earth metal source, at least one
organic solvent, at least one surface interaction enhancing
additive, optionally at least one surfactant, and optionally at
least one chelating agent.
Another aspect of the invention relates to an article of
manufacture comprising a liquid removal composition, a
microelectronic device, and photoresist and/or SARC material
thereon, wherein the liquid removal composition comprises at least
one organic quaternary base, at least one surface interaction
enhancing additive, and optionally at least one component selected
from the group consisting of: at least one alkali or alkaline earth
metal source; at least one organic solvent; at least one
surfactant; at least one chelating agent; and combinations
thereof.
In a further aspect, the present invention relates to a method of
manufacturing a microelectronic device, said method comprising
contacting the microelectronic device with a liquid removal
composition for sufficient time to at least partially remove
photoresist and/or SARC material from the microelectronic device,
wherein the liquid removal composition includes at least one
organic quaternary base, at least one surface interaction enhancing
additive, and optionally at least one component selected from the
group consisting of: at least one alkali or alkaline earth metal
source; at least one organic solvent; at least one surfactant; at
least one chelating agent; and combinations thereof.
Yet another aspect of the invention relates to improved
microelectronic devices, and products incorporating same, made
using the methods of the invention comprising the removal of
photoresist and/or SARC material from the microelectronic device
having said material thereon, using the methods and/or compositions
described herein, and optionally, incorporating the microelectronic
device into a product.
A still further aspect of the invention relates to a liquid removal
composition comprising at least one co-solvent and at least one
surface interaction enhancing additive, wherein said surface
interaction enhancing additive comprises a species selected from
the group consisting of poly(acrylamide-co-diallyldiemthylammonium
chloride), poly(acrylamide), poly(acrylic acid),
poly(diallyldiemthylammonium chloride), diallyldimethylammonium
chloride, acrylamide, acetoguanamine, and combinations thereof, and
wherein said removal composition is useful for removing photoresist
and/or sacrificial anti-reflective coating (SARC) materials from a
microelectronic device having such material(s) thereon. Preferably,
the removal composition is devoid of abrasive and is not
supercritical or subcritical.
Other aspects, features and embodiments of the invention will be
more fully apparent from the ensuing disclosure and appended
claims.
DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS
THEREOF
The present invention contemplates liquid removal compositions that
are useful to remove photoresist and/or sacrificial anti-reflective
coating (SARC) materials from a microelectronic device having such
material(s) thereon.
For ease of reference, "microelectronic device" corresponds to
semiconductor substrates, flat panel displays, and
microelectromechanical systems (MEMS), manufactured for use in
microelectronic, integrated circuit, or computer chip applications.
It is to be understood that the term "microelectronic device" is
not meant to be limiting in any way and includes any substrate that
will eventually become a microelectronic device or microelectronic
assembly.
As defined herein, "low-k dielectric material" corresponds to any
material used as a dielectric material in a layered microelectronic
device, wherein the material has a dielectric constant less than
about 3.5. Preferably, the low-k dielectric materials include
low-polarity materials such as silicon-containing organic polymers,
silicon-containing hybrid organic/inorganic materials,
organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG),
silicon dioxide, and carbon-doped oxide (CDO) glass. It is to be
appreciated that the low-k dielectric materials may have varying
densities and varying porosities.
As used herein, "about" is intended to correspond to .+-.5% of the
stated value.
As used herein, "suitability" for removing photoresist and/or SARC
materials from a microelectronic device having said material(s)
thereon corresponds to at least partial removal of said material(s)
from the microelectronic device. Preferably, at least about 90% of
the material(s), more preferably at least 95% of the material(s),
and most preferably at least 99% of the material(s), is removed
from the microelectronic device using the compositions of the
invention.
As defined herein, "photoresist" includes, but is not limited to,
developed and undeveloped photoresist material, photoresist that
has been plasma etched, e.g., hardened during BEOL dual-damascene
processing of integrated circuits, and/or photoresist that has been
ion implanted, e.g., during front-end-of-line (FEOL) processing to
implant dopant species in the appropriate layers of the
semiconductor wafer. Photoresist that has ion implanted during FEOL
processing may include species selected from the group consisting
of boron, arsenic and phosphorus and as such, the post-etch residue
may include said species.
"Post-etch residue," as used herein, corresponds to material
remaining following gas-phase plasma etching processes, e.g., BEOL
dual-damascene processing. The post-etch residue may be organic,
organometallic, organosilicic, or inorganic in nature, for example,
silicon-containing material, nitrogen-containing material,
oxygen-containing material, polymeric residue material,
copper-containing residue material, etch gas residue such as
chlorine and fluorine, and combinations thereof.
Compositions of the invention may be embodied in a wide variety of
specific formulations, as hereinafter more fully described.
Importantly, the liquid removal compositions of the present
invention must possess good metal compatibility, e.g., a low etch
rate on the metal. Metals of interest include, but are not limited
to, copper, tungsten, cobalt, aluminum, tantalum, molybdenum,
nickel, ruthenium, silicides thereof, alloys thereof, and
combinations thereof.
In all such compositions, wherein specific components of the
composition are discussed in reference to weight percentage ranges
including a zero lower limit, it will be understood that such
components may be present or absent in various specific embodiments
of the composition, and that in instances where such components are
present, they may be present at concentrations as low as 0.001
weight percent, based on the total weight of the composition in
which such components are employed.
In one aspect, the present invention relates to liquid removal
compositions useful in removing photoresist and/or SARC layers from
a microelectronic device substrate. Broadly, the formulation of the
present invention includes at least one organic quaternary base,
water, optionally at least one alkali or alkaline earth metal
source, optionally at least one solvent, amine or combination
thereof, optionally at least one chelator/passivation agent,
optionally at least one surface interaction enhancing additive, and
optionally at least one surfactant. The formulation may include at
least one organic quaternary base, water, at least one surface
interaction enhancing additive, optionally at least one alkali or
alkaline earth metal source, optionally at least one solvent, amine
or combination thereof, optionally at least one
chelator/passivation agent, and optionally at least one surfactant.
In one embodiment, the formulation includes at least one organic
quaternary base, water, at least one alkali or alkaline earth metal
source, at least one solvent, amine or combination thereof, and at
least one chelator/passivation agent. In another embodiment, the
formulation includes at least one organic quaternary base, water,
at least one alkali or alkaline earth metal source, at least one
solvent, amine or combination thereof, at least one surface
interaction enhancing additive, optionally at least one
chelator/passivation agent, and optionally at least one surfactant.
Still another embodiment relates to a formulation including at
least one organic quaternary base, water, at least one alkali or
alkaline earth metal source, at least one chelator/passivation
agent, and at least one surface interaction enhancing additive. In
still another embodiment, the formulation includes at least one
organic quaternary base, water, at least one alkali or alkaline
earth metal source, at least one surface interaction enhancing
additive, and at least one surfactant. In another embodiment, the
formulation includes at least one organic quaternary base, water,
at least one solvent, ainine or combination thereof, at least one
surface interaction enhancing additive, and at least one
surfactant. In still another embodiment, the formulation includes
at least one organic quaternary base, water, at least one alkali or
alkaline earth metal source, at least one solvent, amine or
combination thereof, at least one surface interaction enhancing
additive, and at least one surfactant. In yet another embodiment,
the formulation includes at least one organic quaternary base,
water, at least one alkali or alkaline earth metal source, at least
one solvent, amine or combination thereof, at least one
chelator/passivation agent, and at least one surface interaction
enhancing additive.
Broadly, the formulation of the present invention includes the
following components, present in the following ranges, based on the
total weight of the composition:
TABLE-US-00001 component of % by weight organic quaternary base(s)
about 0.01% to about 30.0% alkali or alkaline earth metal source(s)
0 to about 5.0% solvent(s), amine(s) or combination 0 to about
90.0% thereof chelator/passivation agent(s) 0% to about 10.0%
surfactant(s) 0% to about 10.0% surface interaction enhancing
additive(s) 0% to about 10.0% water 0.01% to about 98.0%
The lower limit of each optional component, when present, is about
0.01 wt %, with the exception of the alkali or alkaline earth metal
source(s), which may be as low as about 0.001 wt %.
In the broad practice of the invention, the liquid removal
composition may comprise, consist of, or consist essentially of:
(i) organic quaternary base(s), water, alkali or alkaline earth
metal source(s), solvent(s), amine(s) or combinations thereof, and
chelator/passivation agent(s); (ii) organic quaternary base(s),
water, alkali or alkaline earth metal source(s), solvent(s),
amine(s) or combinations thereof, surface interaction enhancing
additive(s), optional chelator/passivation agent(s), and optional
surfactant(s); (iii) organic quaternary base(s), water, alkali or
alkaline earth metal source(s), chelator/passivation agent(s), and
surface interaction enhancing additive(s); (iv) organic quaternary
base(s), water, ne alkali or alkaline earth metal source(s),
surface interaction enhancing additive(s), and surfactant(s); (v)
organic quaternary base(s), water, solvent(s), amine(s) or
combinations thereof, surface interaction enhancing additive(s),
and surfactant(s); (vi) organic quaternary base(s), water, alkali
or alkaline earth metal source(s), solvent(s), amine(s) or
combinations thereof, surface interaction enhancing additive(s),
and surfactant(s); (vii) organic quaternary base(s), water, alkali
or alkaline earth metal source(s), solvent(s), amine(s) or
combinations thereof, chelator/passivation agent(s), and surface
interaction enhancing additive(s); or (viii) organic quaternary
base(s), water, surface interaction enhancing additive(s), optional
alkali or alkaline earth metal source(s), optional solvent(s),
amine(s) or combinations thereof, optional chelator/passivation
agent(s), and optional surfactant(s). In general, the specific
proportions and amounts of the components, in relation to each
other, may be suitably varied to provide the desired removal action
of the liquid removal composition for the photoresist and/or SARC
layer species and/or processing equipment, as readily determinable
within the skill of the art without undue effort.
Compositions of the invention may be embodied in a wide variety of
specific formulations, as hereinafter more fully described. In
addition, when the compositions are formulated for the removal of
photoresist and/or SARC layers from a microelectronic device
substrate, the compositions are substantially devoid of abrasive,
e.g., alumina, silica, titania, ceria, zirconia, germania,
magnesia, co-formed products thereof, and combinations thereof,
fluoride species, and oxoammonium compounds such as hydroxylamine
and derivatives of hydroxylamine. "Substantially devoid" is defined
herein as less than 2 wt. %, preferably less than 1 wt. %, more
preferably less than 0.5 wt. %, even more preferably less than 0.1
wt. %, and most preferably less than about 0.01%.
Compositions of the invention have a pH in a range from about 11 to
about 14, preferably about 12 to about 14.
In one specific embodiment, the liquid removal composition includes
the following components:
TABLE-US-00002 component of % by weight organic quaternary base(s)
about 2.0% to about 15.0% alkali or alkaline earth metal source(s)
about 0.001% to about 2.0% solvent(s) about 0.01% to about 90.0%
chelator/passivation agent(s) 0.01% to about 5.0% water about 5.0%
to about 40.0%
wherein percentages of the components are percentages by weight,
based on total weight of the composition, and wherein the total of
the weight percentages of such components of the composition does
not exceed 100 weight %. In a preferred embodiment, the liquid
removal composition includes about 0.01% to about 1.0%
chelator/passivating agent.
In yet another embodiment, the liquid removal composition includes
the following components:
TABLE-US-00003 component of % by weight organic quaternary base(s)
about 2.0% to about 15.0% alkali or alkaline earth metal source(s)
about 0.001% to about 2.0% solvent(s), amine(s) or combination
about 0.01% to about 90.0% thereof chelator/passivation agent(s) 0%
to about 5.0% surfactant(s) 0% to about 5.0% surface interaction
enhancing additive(s) 0.01% to about 5.0% water about 1.0% to about
40.0%
wherein percentages of the components are percentages by weight,
based on total weight of the composition, and wherein the total of
the weight percentages of such components of the composition does
not exceed 100 weight %.
In a preferred embodiment, the composition includes surfactant at a
concentration of about 0.01 wt. % to about 5.0 wt. %.
Such compositions may optionally include additional components,
including active as well as inactive ingredients, e.g.,
stabilizers, dispersants, anti-oxidants, penetration agents,
adjuvants, additives, fillers, excipients, etc.
Organic quaternary bases contemplated herein include, but are not
limited to, (NR.sup.1R.sup.2R.sup.3R.sup.4)OH where R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 may be the same as or different from
one another and each is independently selected from the group
consisting of: hydrogen; straight-chained or branched
C.sub.1-C.sub.7 alkyl groups, e.g., methyl, ethyl, propyl, butyl,
pentyl, hexyl and heptyl; C.sub.6-C.sub.10 aryl groups, e.g.,
benzyl; alcohol groups; any carbon-based organic group such as
alkenes, alkynes, etc., wherein the alkyl, alcohol and carbon-based
groups may be linear and/or branched and all groups may be
substituted; and combinations thereof. The term "aryl" is intended
to be broadly construed as referring to carbocyclic (e.g., phenyl,
naphthyl) groups and encompassing unsubstituted as well as
substituted aryl groups. An example of tetraalkylammonium hydroxide
with an alcohol group includes choline. Examples of substituents
for substituted aryl groups include one or more of C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 alkoxy, and hydroxyl. Preferably, the
organic quaternary base includes tetrabutylammonium hydroxide
(TBAH), benzyltrimethylammonium hydroxide (BTMAH),
tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
tetramethylammonium hydroxide (TMAH), and combinations thereof.
Compositions of such type in which the alkali or alkaline earth
metal source component includes potassium hydroxide, potassium
chloride, other potassium salts having an anion commensurate in
size with the chloride and hydroxide ions, and combinations
thereof. which are especially advantageous in achieving high
efficiency cleaning without adverse effect on the dielectric layer.
Other alkali or alkaline earth metal salts are contemplated, with
the proviso that the alkali or alkaline earth metal cation has an
ionic radius greater than or equal to the ionic radius of
potassium.
Suitable solvent species for such composition include, without
limitation: amines such as monoethanolamine, triethanolamine,
triethylenediamine, methylethanolamine, methyldiethanolamine,
pentamethyldiethylenetriamine, dimethyldiglycolamine,
1,8-diazabicyclo[5.4.0]undecene, aminopropylmolpholine,
hydroxyethylmorpholine, aminoethylmorpholine,
hydroxypropylmorpholine, diglycolamine, N-methylpyrrolidinone
(NMP), N-octylpyrrolidinone, N-phenylpyrrolidinone,
cyclohexylpyrrolidinone and vinyl pyrrolidinone; sulfur-containing
solvents such as tetramethylene sulfone; glycols such as ethylene
glycol, propylene glycol (1,2-propanediol) and neopentyl glycol;
glycol ethers such as diethylene glycol monomethyl ether,
triethylene glycol monomethyl ether, diethylene glycol monoethyl
ether, triethylene glycol monoethyl ether, ethylene glycol
monopropyl ether, ethylene glycol monobutyl ether, diethylene
glycol monobutyl ether, triethylene glycol monobutyl ether,
ethylene glycol monohexyl ether, diethylene glycol monohexyl ether,
ethylene glycol phenyl ether, propylene glycol methyl ether,
dipropylene glycol methyl ether, tripropylene glycol methyl ether,
propylene glycol n-propyl ether, dipropylene glycol n-propyl ether,
tripropylene glycol n-propyl ether, propylene glycol n-butyl ether,
dipropylene glycol n-butyl ether, tripropylene glycol n-butyl
ether, and propylene glycol phenyl ether (phenoxy-2-propanol); and
combination thereof. Preferably, the solvent species includes
1,2-propanediol, phenoxy-2-propanol, hydroxyethylmorpholine and
di(ethylene glycol) methyl ether.
The chelator/passivation agent in such composition can be of any
suitable type, and may include, without limitation, triazoles, such
as 1,2,4-triazole, or triazoles substituted with substituents such
as C.sub.1-C.sub.8 alkyl, amino, thiol, mercapto, imino, carboxy
and nitro groups, such as benzotriazole, tolyltriazole,
5-phenyl-benzotriazole, 5-nitro-benzotriazole,
3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole,
hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole,
1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole,
3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole,
3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole,
halo-benzotriazoles (halo=F, Cl, Br or I), naphthotriazole, and the
like, as well as thiazoles, tetrazoles, imidazoles, phosphates,
thiols and azines such as 2-mercaptobenzoimidizole,
2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole,
2-mercaptothiazoline, 5-aminotetrazole,
5-amino-1,3,4-thiadiazole-2-thiol,
2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine,
methyltetrazole, 1,3-dimethyl-2-imidazolidinone,
1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,
diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione,
inercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol,
5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl
phosphate, indiazole, etc. Suitable chelator species further
include glycerols, amino acids, carboxylic acids, alcohols, amides
and quinolines such as guanine, urea, adenine, glycerol,
thioglycerol, nitrilotriacetic acid, salicylamide, benzoguanamine,
melamine, thiocyranuric acid, anthranilic acid, gallic acid,
ascorbic acid, salicylic acid, 8-hydroxyquinoline, 5-carboxylic
acid-benzotriazole, 3-mercaptopropanol, boric acid, iminodiacetic
acid, etc. The chelator is usefully employed to increase the
compatibility of the composition with the metals and the dielectric
materials used in the semiconductor device. Preferably, the
chelator is 2-mercaptobenzimidazole.
Suitable surfactants in the liquid removal compositions of the
present invention may include bis-(2-hydroxyethyl)
isodecyloxypropylamine oxide, alkoxylated ether amine oxides, as
described in U.S. Pat. No. 5,972,875 in the name of Crutcher et
al., such as TOMAH AO-455, AO-405, and ether amine oxides derived
from a branched chain C.sub.10 alcohol such as TOMAH AO-14-2.
Although not wishing to be bound by theory, it is thought that the
surface interaction enhancing additives coordinate with the
hydroxide compounds to increase their ability to efficiently remove
the SARC layer material. Surface interaction enhancing additives
include, but are not limited to,
poly(acrylamide-co-diallyldimethylammonium chloride),
poly(acrylamide), poly(acrylic acid), poly(diallyldimethylammonium
chloride), diallyldimethylammonium chloride, acrylamide,
acetoguanamine, and combinations thereof.
In various preferred embodiments, the liquid removal composition is
formulated in the following Formulations A-W, wherein all
percentages are by weight, based on the total weight of the
formulation: Formulation A: 3.6% BTMAH; 0.27% potassium hydroxide;
0.08% 2-mercaptobenzimidazole; 15.73% water; 18.83%
phenoxy-2-propanol; 56.49% 1,2-propanediol; 5%
hydroxyethylmorpholine Formulation B: 3.6% BTMAH; 0.27% potassium
hydroxide; 0.08% 2-mercaptobenzimidazole; 15.73% water; 18.83%
phenoxy-2-propanol; 56.49% 1,2-propanediol; 5%
cyclohexylpyrrolidinone Formulation C: 4.8% BTMAH; 0.27% potassium
hydroxide; 0.08% 2-mercaptobenzimidazole; 17.53% water; 42.19%
phenoxy-2-propanol; 30.13% 1,2-propanediol; 5%
hydroxyethylmorpholine Formulation D: 6.0% BTMAH; 0.27% potassium
hydroxide; 0.08% 2-mercaptobenzimidazole; 19.33% water; 40.41%
phenoxy-2-propanol; 28.91% 1,2-propanediol; 5%
hydroxyethylmorpholine Formulation E: 4.8% BTMAH; 0.27% potassium
hydroxide; 0.08% 2-mercaptobenzimidazole; 17.53% water; 39.25%
phenoxy-2-propanol; 28.07% 1,2-propanediol; 10%
hydroxyethylmorpholine Formulation F: 3.6% BTMAH; 0.27% potassium
hydroxide; 1.25% TMAH; 0.08% 2-mercaptobenzimidazole; 19.48% water;
41.00% phenoxy-2-propanol; 29.32% 1,2-propanediol; 5%
hydroxyethylmorpholine Formulation G: 3.6% BTMAH; 0.27% potassium
hydroxide; 2.5% TMAH; 0.08% 2-mercaptobenzimidazole; 23.23% water;
38.08% phenoxy-2-propanol; 27.24% 1,2-propanediol; 5%
hydroxyethylmorpholine Formulation H, 3.6% BTMAH; 0.27% potassium
hydroxide; 1.25% TMAH; 0.08% 2-mercaptobenzimidazole; 19.48% water;
38.08% phenoxy-2-propanol; 27.24% 1,2-propanediol; 10%
hydroxyethylmorpholine Formulation I: 1.6% BTMAH; 0.27% potassium
hydroxide; 2.5% TMAH; 0.08% 2-mercaptobenzimidazole; 10.23% water;
49.74% phenoxy-2-propanol; 35.58% 1,2-propanediol Formulation J:
1.6% BTMAH; 0.27% potassium hydroxide; 2.5% TMAH; 0.08%
2-mercaptobenzimidazole; 20.23% water; 43.91% phenoxy-2-propanol;
31.41% 1,2-propanediol Formulation K: 1.6% BTMAH; 0.27% potassium
hydroxide; 2.5% TMAH; 0.08% 2-mercaptobenzimidazole; 20.23% water;
41.0% phenoxy-2-propanol; 29.32% 1,2-propanediol; 5.0%
tetramethylene sulfone Formulation L: 1.6% BTMAH; 0.27% potassium
hydroxide; 2.5% TMAH; 0.08% 2-mercaptobenzimidazole; 10.23% water;
5% tetramethylene sulfone; 46.83% phenoxy-2-propanol; 33.49%
1,2-propanediol Formulation M: 3.6% BTMAH; 0.27% potassium
hydroxide; 2.5% TMAH; 0.08% 2-mercaptobenzimidazole; 13.23% water;
5% tetramethylene sulfone; 43.91% phenoxy-2-propanol; 31.41%
1,2-propanediol Formulation N: 3.6% BTMAH; 0.27% potassium
hydroxide; 2.5% TMAH; 0.08% 2-mercaptobenzimidazole; 23.23% water;
5% tetramethylene sulfone; 38.08% phenoxy-2-propanol; 27.24%
1,2-propanediol Formulation O: 3.6% BTMAH; 0.27% potassium
hydroxide; 2.5% TMAH; 0.08% 2-mercaptobenzimidazole; 18.23% water;
5% tetramethylene sulfone; 41.00% phenoxy-2-propanol; 29.32%
1,2-propanediol Formulation P: 3.34% BTMAH; 0.27% potassium
hydroxide; 1.19% TMAH; 0.08% 2-mercaptobenzimidazole; 8.92% water;
17.24% tetramethylene sulfone; 51.72% 1,2-propanediol; 17.24%
di(ethylene glycol) methyl ether Formulation Q: 4.0% BTMAH; 0.27%
potassium hydroxide; 2.0% TMAH; 0.08% 2-mercaptobenzimidazole;
7.25% water; 25% tetramethylene sulfone; 51.4% 1,2-propanediol; 10%
di(ethylene glycol) methyl ether Formulation R: 3.46% BTMAH; 0.36%
potassium hydroxide; 1.5% TMAH; 0.08% 2-mercaptobenzimidazole;
10.05% water; 30% tetramethylene sulfone; 5% phenoxy-2-propanol;
34.55% 1,2-propanediol; 15% di(ethylene glycol) methyl ether
Formulation S: 3.46% BTMAH; 0.27% potassium hydroxide; 1.5% TMAH;
0.08% 2-mercaptobenzimidazole; 9.94% water; 20% tetramethylene
sulfone; 5% phenoxy-2-propanol; 44.75% 1,2-propanediol; 15%
di(ethylene glycol) methyl ether Formulation T: 3.46% BTMAH; 0.27%
potassium hydroxide; 1.5% TMAH; 0.08% 2-mercaptobenzimidazole;
10.02% water; 25% tetramethylene sulfone; 5% phenoxy-2-propanol;
39.67% 1,2-propanediol; 15% di(ethylene glycol) methyl ether
Formulation U: 3.46% BTMAH; 0.36% potassium hydroxide; 1.5% TMAH;
0.08% 2-mercaptobenzimidazole; 10.13% water; 25% tetramethylene
sulfone; 5% phenoxy-2-propanol; 39.47% 1,2-propanediol; 15%
di(ethylene glycol) methyl ether Formulation V: 3.73% BTMAH; 0.27%
potassium hydroxide; 1.5% TMAH; 0.08% 2-mercaptobenzimidazole;
10.425% water; 25% tetramethylene sulfone; 5% phenoxy-2-propanol;
38.995% 1,2-propanediol; 15% di(ethylene glycol) methyl ether
Formulation W: 3.73% BTMAH; 0.36% potassium hydroxide; 1.5% TMAH;
0.08% 2-mercaptobenzimidazole; 10.535% water; 25% tetramethylene
sulfone; 5% phenoxy-2-propanol; 38.795% 1,2-propanediol; 15%
di(ethylene glycol) methyl ether
Further embodiments include cleaning Formulations X-AJ, wherein all
percentages are by weight, based on the total weight of the
formulation. Formulations X-AJ all contain 15% di(ethylene glycol)
methyl ether, 25% tetramethylene sulfone, 5% phenoxy-2-propanol,
0.08% 2-mercaptobenzimidazole, 0.27% potassium hydroxide and the
listed percentages of BTMAH, TMAH, water and propylene glycol.
TABLE-US-00004 Formulation BTMAH % TMAH % Water % Propylene Glycol
% X 1.5 0.4 9.5 43.25 Y 1.5 1.1 9.5 42.55 Z 2.5 0.4 9.5 42.25 AA
2.5 1.1 9.5 41.55 AB 1.5 0.75 6.0 46.4 AC 1.5 0.75 13.0 39.4 AD 2.5
0.75 6.0 45.4 AE 2.5 0.75 13.0 38.4 AF 2.0 0.4 6.0 46.25 AG 2.0 0.4
13.0 39.25 AH 2.0 1.1 6.0 45.55 AI 2.0 1.1 13.0 38.55 AJ 2.0 0.75
9.5 42.4
Further embodiments include cleaning Formulations AK-AQ, wherein
all percentages are by weight, based on the total weight of the
formulation. Formulations AK-AQ all contain 3.73%
benzyltrimethylammonium hydroxide, 1.5% TMAH, 0.08%
2-mercaptobenzimidazole, 0.27% potassium hydroxide, 5%
phenoxy-2-propanol and 12.5% water and the listed percentages of
tetramethylene sulfone, di(ethylene glycol) methyl ether, and
propylene glycol.
TABLE-US-00005 Tetramethylene Di(ethylene glycol) Propylene
Formulation sulfone % methyl ether % Glycol % AK 25.0 22.5 29.42 AL
25.0 30.0 21.92 AM 25.0 37.5 14.42 AN 25.0 45.0 6.92 AO 15.0 30.0
31.92 AP 15.0 45.0 16.92 AQ 15.0 60.0 1.92
In yet another embodiment, the liquid removal composition includes
Formulations BA-BN, wherein all percentages are by weight, based on
the total weight of the formulation. Formulations BA-BN all contain
3.0% BTMAH, 0.2925% potassium hydroxide, and corresponding amounts
of the components listed.
TABLE-US-00006 poly(acrylamide-co- Di(ethylene diallyldimethyl
ammonium glycol) methyl Formulation chloride) % ether % Water % BA
0.075 0 96.6325 BB 0.1 0 96.6075 BC 0.125 0 96.5825 BD 0.15 0
96.5575 BE 0.175 0 96.5325 BF 0.2 0 96.5075 BG 0.25 0 96.4575 BH
0.3 0 96.4075 BI 0.4 0 96.3075 BJ 0.5 0 96.2075 BK 0.15 2 94.5575
BL 0.15 4 92.5575 BM 0.15 6 90.5575 BN 0.15 8 88.5575
In still another embodiment, the liquid removal composition
includes Formulations BO-BT, wherein all percentages are by weight,
based on the total weight of the formulation. Formulations BO-BT
all contain 3.0% BTMAH, 0.2925% potassium hydroxide, and
corresponding amounts of the components listed.
TABLE-US-00007 Formulation Additive Additive amount % Water % BO
Polyacrylamide 0.05 96.6575 BP 0.1 96.6075 BQ 0.2 96.5075 BR
Poly(acrylic acid) 0.05 96.6575 BS 0.1 96.6075 BT 0.2 96.5075
In still another embodiment, the liquid removal composition
includes Formulations BU-BZ, wherein all percentages are by weight,
based on the total weight of the formulation. Formulations BU-BZ
all contain 3.0% BTMAH, 0.2925% potassium hydroxide, 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), and
corresponding amounts of the components listed.
TABLE-US-00008 Formulation 2-mercaptobenzimidazole % Water % BU
0.05 96.5075 BV 0.075 96.4825 BW 0.1 96.4575 BX 0.15 96.4075 BY 0.2
96.3575 BZ 0.25 96.3075
In another embodiment, the liquid removal composition includes
Formulations BA.sup.2-BH.sup.2, wherein all percentages are by
weight, based on the total weight of the formulation. Formulations
BA.sup.2-BH.sup.2 all contain 3.0% BTMAH, 0.2925% potassium
hydroxide, 0.15% poly(acrylamide-co-diallyldimethyl ammonium
chloride), and corresponding amounts of the components listed.
TABLE-US-00009 Formulation Surfactant Surfactant amount % Water %
BAA Tomah AO-14-2 0.08 96.4775 BBB 0.1 96.4575 BCC 0.12 96.4375 BDD
0.14 96.4175 BEE Tomah AO-405 0.08 96.4775 BFF 0.1 96.4575 BGG 0.12
96.4375 BHH 0.14 96.4175
In yet another embodiment, the liquid removal composition includes
Formulations BI.sup.2-BR.sup.2, wherein all percentages are by
weight, based on the total weight of the formulation. Formulations
BI.sup.2-BR.sup.2 all contain 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), 0.1% Tomah
AO-405, and corresponding amounts of the components listed.
TABLE-US-00010 Formulation BTMAH % KOH % Water % BII 1.5 0.18 98.07
BJJ 1.5 0.405 97.845 BKK 3.0 0.18 96.57 BLL 3.0 0.405 96.345 BMM
2.25 0.2925 97.2075 BNN 2.25 0.2925 97.2075 BOO 1.5 0.2925 97.9575
BPP 3.0 0.2925 96.4575 BQQ 2.25 0.18 97.32 BRR 2.25 0.405
97.095
In still another embodiment, the liquid removal composition
includes Formulations BS.sup.2-BB.sup.3, wherein all percentages
are by weight, based on the total weight of the formulation.
Formulations BS.sup.2-BB.sup.3 all contain 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), 0.1% Tomah
AO-405, 5.2% BTMAH and corresponding amounts of the components
listed.
TABLE-US-00011 tetramethylene di(ethylene glycol) Formulation
sulfone % methyl ether % Water % BSS 10 15 69.55 BTT 20 15 59.55
BUU 10 30 54.55 BVV 20 30 44.55 BWW 15 22.5 57.05 BXX 15 22.5 57.05
BYY 15 15 64.55 BZZ 15 30 49.55 BAAA 10 22.5 62.05 BBBB 20 22.5
52.05
In another embodiment, the liquid removal composition includes
Formulations BC.sup.3-BH.sup.3, wherein all percentages are by
weight, based on the total weight of the formulation. Formulations
BC.sup.3-BH.sup.3 all contain 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), 0.1% Tomah
AO-455, 8.25% tetrabutylammonium hydroxide, 10% tetramethylene
sulfone, 20% di(ethylene glycol) methyl ether, and corresponding
amounts of the components listed.
TABLE-US-00012 Formulation water % propylene glycol % BCCC 10 51.5
BDDD 20 41.5 BEEE 30 31.5 BFFF 40 21.5 BGGG 50 11.5 BHHH 60 1.5
In another embodiment of the invention, the liquid removal
composition includes Formulations BI.sup.3-BM.sup.3, wherein all
percentages are by weight, based on the total weight of the
formulation. Formulations BI.sup.3-BM.sup.3 all contain 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), 0.1% Tomah
AO-405, 8.25% tetrabutylammonium hydroxide, 22% tetramethylene
sulfone, 27% di(ethylene glycol) methyl ether, and corresponding
amounts of the components listed.
TABLE-US-00013 Formulation water % propylene glycol % BIII 10 32.5
BJJJ 20 22.5 BKKK 30 12.5 BLLL 40 2.5 BMMM 42.5 0
In yet another embodiment of the invention, the liquid removal
composition includes Formulations BN.sup.3-BS.sup.3, wherein all
percentages are by weight, based on the total weight of the
formulation. Formulations BN.sup.3-BS.sup.3 all contain 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), 0.1% Tomah
AO-405, 20% tetramethylene sulfone, 10% di(ethylene glycol) methyl
ether, 60% water and corresponding amounts of the components
listed.
TABLE-US-00014 tetrabutylammonium Formulation hydroxide % propylene
glycol % BNNN 8.25 1.5 BOOO 7.15 2.6 BPPP 6.05 3.7 BQQQ 4.95 4.8
BRRR 3.85 5.9 BSSS 2.75 7.0
In still another embodiment of the invention, the liquid removal
composition includes Formulations BT.sup.3-CE, wherein all
percentages are by weight, based on the total weight of the
formulation. Formulations BT.sup.3-CE all contain 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), 0.1% Tomah
AO-405, and corresponding amounts of the components listed, wherein
the tetramethylene sulfone:di(ethylene glycol) methyl ether
solution has a ratio of 22:27.
TABLE-US-00015 tetramethylene sulfone:di(ethylene glycol)
Formulation BTMAH % water % methyl ether % BTTT 4.6 66 29.15 BUUU
56 19.15 BVVV 46 9.15 BWWW 4.1 66 29.65 BXXX 56 19.65 BYYY 46 9.65
BZZZ 3.6 66 30.15 CA 56 20.15 CB 46 10.15 CC 3.1 66 30.65 CD 56
20.65 CE 46 10.65
In another embodiment of the invention, the liquid removal
composition includes Formulations CF-CQ, wherein all percentages
are by weight, based on the total weight of the formulation.
Formulations CF-CQ all contain 0.15%
poly(acrylamide-co-diallyldimethyl ammonium chloride), 0.1% Tomah
AO-405, 22% tetramethylene sulfone, 27% di(ethylene glycol) methyl
ether, and corresponding amounts of the components listed.
TABLE-US-00016 potassium Formulation BTMAH % water % hydroxide/ppm
CF 4.6 46 0 CG 46 90 CH 46 180 CI 3.2 46 0 CJ 46 90 CK 46 180 CL
4.6 32 0 CM 32 90 CN 32 180 CO 3.2 32 0 CP 32 90 CQ 32 180
In another embodiment of the invention, the liquid removal
composition includes Formulation CR and CS, wherein CR contains
0.15% poly(acrylamide-co-diallyldimethyl ammonium chloride), 22%
sulfolane, 27% di(ethylene glycol) methyl ether, 2.9% BTMAH, 0.018%
KOH, 17.9% propylene glycol, 0.08% MBI, and 29.95% water, and CS
contains 0.15% poly(acrylamide-co-diallyldimethyl ammonium
chloride), 22% sulfolane, 27% di(ethylene glycol) methyl ether,
2.9% BTMAH, 0.009% KOH, 17.9% propylene glycol, 0.08% MBI, and
29.96% water.
In yet another embodiment of the invention, the liquid removal
composition includes at least one quaternary base, potassium
chloride, and at least one chelator/passivating agent enumerated
hereinabove. Preferably, the chelator/passivating agent(s) may be
selected from the group consisting of urea,
2-mercaptobenzimidazole, 1,2,4-triazole, and combinations thereof.
Alternatively, the liquid removal composition includes at least one
quaternary base, potassium chloride, urea, and at least one
additional chelator/passivating agent. This embodiment of the
liquid removal composition includes Formulations DA-DI, wherein all
percentages are by weight, based on the total weight of the
formulation: Formulation DA: 2.9% BTMAH; 0.025% KOH; 22%
di(ethylene glycol) butyl ether; 0.08% 2-mercaptobenzimidazole; 1.5
wt. % urea; 27% sulfolane; 17.9 propylene glycol; 28.595% water
Formulation DB: 2.9% BTMAH; 0.025% KOH; 22% di(ethylene glycol)
methyl ether; 0.08% 2-mercaptobenzimidazole; 1.5 wt. % urea; 27%
sulfolane; 17.9 ethylene glycol; 28.595% water Formulation DC: 2.9%
BTMAH; 0.025% KCl; 22% di(ethylene glycol) methyl ether; 0.08%
2-mercaptobenzimidazole; 1.5 wt. % urea; 27% sulfolane; 17.9
propylene glycol; 28.595% water Formulation DD: 1.5% BTMAH; 0.025%
KOH; 22% di(ethylene glycol) methyl ether; 0.08%
2-mercaptobenzimidazole; 1.5 wt. % urea; 27% sulfolane; 17.9
propylene glycol; 27.995% water Formulation DE: 2.9% BTMAH; 0.025%
KOH; 22% di(ethylene glycol) butyl ether; 0.08%
2-mercaptobenzimidazole; 1.5 wt. % urea; 27% sulfolane; 17.9
ethylene glycol; 28.595% water Formulation DF: 2.9% TMAH; 0.025%
KOH; 22% di(ethylene glycol) methyl ether; 0.08%
2-mercaptobenzimidazole; 1.5 wt. % urea; 27% sulfolane; 17.9
propylene glycol; 28.595% water Formulation DG: 2.9% TMAH; 0.025%
KCl; 22% di(ethylene glycol) methyl ether; 0.08%
2-mercaptobenzimidazole; 1.5 wt. % urea; 27% sulfolane; 17.9
propylene glycol; 28.595% water Formulation DH: 2.9% TMAH; 0.025%
KCl; 22% di(ethylene glycol) butyl ether; 0.08%
2-mercaptobenzimidazole; 1.5 wt. % urea; 27% sulfolane; 17.9
ethylene glycol; 28.595% water Formulation DI: 2.9% TMAH; 0.025%
KCl; 22% di(ethylene glycol) butyl ether; 0.08%
2-mercaptobenzimidazole; 1.5 wt. % urea; 14% sulfolane; 17.9
ethylene glycol; 41.595% water
In yet another embodiment of the invention, the liquid removal
composition includes about 35 to about 65 wt. % 1,2-propanediol,
about 5 to about 25 wt. % tetramethylene sulfone, about 2 to about
15 wt. % phenoxy-2-propanol, about 2 to about 15 wt. % di(ethylene
glycol) methyl ether, about 1 to about 6 wt. %
benzyltrimethylammonium hydroxide, about 0.5 to about 3 wt. %
tetramethylammonium hydroxide, about 0.001 to about 0.3 wt. %
2-mercaptobenzimidazole, about 0.1 to about 0.5 wt. % KOH, and
about 5 to about 50 wt. % water. For example, the liquid removal
composition is formulated in the following Formulations EA-ED,
wherein all percentages are by weight, based on the total weight of
the formulation: Formulation EA: 3.73% BTMAH; 0.27% potassium
hydroxide; 1.5% TMAH; 0.08% 2-mercaptobenzimidazole; 12.777% water;
25% tetramethylene sulfone; 5% phenoxy -2-propanol; 36.64%
1,2-propanediol; 15% di(ethylene glycol) methyl ether Formulation
EB: 3.73% BTMAH; 0.27% potassium hydroxide; 1.5% TMAH; 0.08%
2-mercaptobenzimidazole; 10.39% water; 25% tetramethylene sulfone;
5% phenoxy-2-propanol; 39.032% 1,2-propanediol; 15% di(ethylene
glycol) methyl ether Formulation EC: 3.18% BTMAH; 0.27% potassium
hydroxide; 1.5% TMAH; 0.08% 2-mercaptobenzimidazole; 13% water; 25%
tetramethylene sulfone; 5% phenoxy-2-propanol; 36.976%
1,2-propanediol; 15% di(ethylene glycol) methyl ether Formulation
ED: 3.18% BTMAH; 0.27% potassium hydroxide; 1.5% TMAH; 0.08%
2-mercaptobenzimidazole; 13% water; 20% tetramethylene sulfone; 5%
phenoxy-2-propanol; 41.976% 1,2-propanediol; 15% di(ethylene
glycol) methyl ether
The range of weight percent ratios of the components of the removal
composition, when present, are: about 0.001:1 to about 0.3:1 alkali
or alkaline earth metal source(s) relative to organic quaternary
base(s), more preferably about 0.001:1 to about 0.1:1; about 0.01:1
to about 0.2:1 surface interaction enhancing additive(s) relative
to organic quaternary base(s), preferably about 0.03:1 to about
0.07:1; about 0.01:1 to about 0.07:1 surfactant(s) relative to
organic quaternary base(s), preferably about 0.03:1 to about
0.05:1; about 1:1 to about 65:1 water relative to organic
quaternary base(s), preferably about 2:1 to about 45:1; about 1:1
to about 55:1 solvent(s), amine(s) or combination thereof relative
to organic quaternary base(s), preferably about 10:1 to about 30:1;
and about 0.01:1 to about 0.1:1 chelator/passivation agent(s)
relative to organic quaternary base(s), preferably about 0.01:1 to
about 0.03:1.
In yet another embodiment, any of the broadly or specifically
described removal compositions of the present invention further
include photoresist and/or SARC material residue. Importantly, the
residue material and/or hardmask material may be dissolved and/or
suspended in the cleaning composition of the invention.
The liquid removal compositions of the invention are easily
formulated by simple addition of the respective ingredients and
mixing to homogeneous condition. Furthermore, the liquid removal
compositions may be readily formulated as single-package
formulations or multi-part formulations that are mixed at the point
of use. The individual parts of the multi-part formulation may be
mixed at the tool or in a storage tank upstream of the tool. The
concentrations of the respective ingredients may be widely varied
in specific multiples of the removal composition, i.e., more dilute
or more concentrated, in the broad practice of the invention, and
it will be appreciated that the liquid removal compositions of the
invention can variously and alternatively comprise, consist or
consist essentially of any combination of ingredients consistent
with the disclosure herein.
It will be appreciated that in general removal applications, it is
common practice to make highly concentrated forms to be used at
extreme dilutions. For example, the removal composition may be
diluted at the manufacturer, before use, and/or during use at the
fab. Dilution ratios may be in a range from 1 part diluent: 1 part
removal composition to 200 parts diluent: 1 part removal
composition. It is understood that upon dilution, the weight
percent ratios of the components of the removal composition will
remain unchanged.
Another aspect of the invention relates to a kit including, in one
or more containers, one or more components adapted to form the
liquid removal compositions of the invention. Preferably, the kit
includes, in one or more containers, organic quaternary base(s),
solvent(s), optional alkali or alkaline earth metal source(s),
optional chelator/passivation agent(s), optional surfactant(s), and
optional surface interaction enhancing additive(s), for combining
with the optional water at the fab. Other combinations of liquid
removal composition components are contemplated herein. The
containers of the kit should be chemically rated to store and
dispense the component(s) contained therein. For example, the
containers of the kit may be NOWPak.RTM. containers (Advanced
Technology Materials, Inc., Danbury, Conn., USA).
In cleaning application, the liquid removal composition is applied
in any suitable manner to the material to be cleaned, e.g., by
spraying the liquid removal composition on the surface of the
material to be cleaned, by dipping (in a volume of the liquid
removal composition) of the material or article including the
material to be cleaned, by contacting the material or article to be
cleaned with another material, e.g., a pad, or fibrous sorbent
applicator element, that has the liquid removal composition
absorbed thereon, by contacting the material or article including
the material to be cleaned with a circulating liquid removal
composition, or by any other suitable means, manner or technique,
by which the liquid removal composition is brought into cleaning
contact with material to be cleaned.
As applied to microelectronic device manufacturing operations, the
liquid removal compositions of the present invention are usefully
employed to remove photoresist and/or SARC materials from
substrates and microelectronic device structures on which such
material(s) have been deposited.
It is to be understood that the phrase "removing photoresist and/or
SARC materials from a microelectronic device" is not meant to be
limiting in any way and includes the removal of photoresist and/or
SARC materials from any substrate that will eventually become a
microelectronic device.
The compositions of the present invention, by virtue of their
selectivity for such photoresist and/or SARC materials, relative to
other materials that may be present on the microelectronic device
substrate and exposed to the liquid removal composition, such as
ILD structures, metallization, barrier layers, etc., achieve at
least partial removal of the photoresist and/or SARC material(s) in
a highly efficient manner.
Importantly, the compositions of the present invention have a low
amount of water and as such, are compatible with copper, aluminum
and cobalt layers, preferably less than 50 wt % water, more
preferably less than 40 wt % water, even more preferably less than
30 wt % water and even more preferably less than 25 wt % water. The
copper and/or cobalt etch rates in the presence of the compositions
of the invention are less than 5 .ANG./min, preferably less than 2
.ANG./min, most preferably less than 1 .ANG./min.
In use of the compositions of the invention for removing
photoresist and/or SARC materials from microelectronic device
substrates having same thereon, the liquid removal composition
typically is contacted with the device substrate for a time of from
about 1 to about 60 minutes, preferably about 20 to about 30
minutes, at temperature in a range of from about 50.degree. C. to
about 80.degree. C. Such contacting times and temperatures are
illustrative, and any other suitable time and temperature
conditions may be employed that are efficacious to at least
partially remove the photoresist and/or SARC material from the
device substrate, within the broad practice of the invention. As
defined herein, "at least partial removal" corresponds to at least
50% removal of photoresist and/or SARC material, preferably at
least 80% removal of photoresist and/or SARC material. Most
preferably, at least 90% of the photoresist and/or SARC material is
removed using the compositions of the present invention.
Following the achievement of the desired cleaning action, the
liquid removal composition is readily removed from the substrate or
article to which it has previously been applied, e.g., by rinse,
wash, or other removal step(s), as may be desired and efficacious
in a given end use application of the compositions of the present
invention. For example, the device may be rinsed with a rinse
solution including deionized water and/or dried (e.g., spin-dry,
N.sub.2, vapor-dry etc.).
In yet another embodiment, the liquid removal composition of the
invention may be utilized in other aspects of the microelectronic
device manufacturing process, i.e., subsequent to removal of
photoresist and/or SARC material processing step. For example, the
liquid removal compositions may be diluted and used as a
post-chemical mechanical polishing (CMP) clean.
Alternatively, the cleaning compositions of the invention may be
combined with abrasive material and used as a Step II CMP slurry.
Step II CMP slurries typically have a high barrier material removal
rate relative to the removal rate of copper and dielectric
material. For example, abrasive material may be added to the
cleaning compositions of the invention (to yield a cleaning
composition slurry) and used for the CMP of a microelectronic
device having tungsten and Ti/TiN barrier layer materials thereon.
If the microelectronic device comprises copper material, a copper
inhibiting species is preferably added to the cleaning composition
slurry to protect the copper during planarization processes.
Abrasives contemplated herein includes silica, alumina, ceria and
mixtures thereof Inhibitors contemplated herein include imidazole,
aminotetrazole, benzotriazole, benzimidazole, amino, imino,
carboxy, mercapto, nitro, alkyl, urea and thiourea compounds,
oxalic acid, malonic acid, succinic acid, nitrilotriacetic acid,
iminodiacetic acid, and combinations thereof. Preferably, the
alternative Step II CMP composition comprises abrasive(s),
inhibitor(s), organic quaternary base(s), alkali or alkaline earth
metal base(s), co-solvent(s), optionally surfactant(s), and
optionally chelating agent(s).
Yet another aspect of the invention relates to the improved
microelectronic devices made according to the methods of the
invention and to products containing such microelectronic
devices.
A still further aspect of the invention relates to methods of
manufacturing an article comprising a microelectronic device, said
method comprising contacting the microelectronic device with a
liquid removal composition for sufficient time to at least
partially remove photoresist and/or SARC materials from the
microelectronic device having said photoresist and/or SARC
materials thereon, and incorporating said microelectronic device
into said article, wherein the liquid removal composition includes
at least one organic quaternary base, water, optionally at least
one alkali or alkaline earth metal source, optionally at least one
solvent, amine, or combination thereof, optionally at least one
chelator/passivation agent, optionally at least one surfactant, and
optionally at least one surface interaction enhancing additive.
The features and advantages of the invention are more fully shown
by the illustrative examples discussed below.
EXAMPLE 1
Photoresist and SARC removal was performed on samples of patterned
low-k dielectric substrate including photoresist and SARC layers.
The samples were dipped in removal solutions X-AJ for 30 minutes at
60.degree. C. and then rinsed with copious amounts of deionized
water and dried under nitrogen. The percent removal of photoresist
and SARC material from the patterned wafer was approximated using
scanning electron microscopy. The results are tabulated in Table 1
hereinbelow.
TABLE-US-00017 TABLE 1 Cleaning results for formulations X-AJ.
Formulation Percent Cleaning X 85% Y 98% Z 98% AA 99% AB 99% AC 99%
AD 97% AE 99% AF 67% AG 99% AH 83% AI 93% AJ 87%
EXAMPLE 2
Photoresist and SARC removal was performed on samples of patterned
low-k dielectric substrate including photoresist and SARC layers.
The samples were dipped in removal solutions AK-AQ for 30 minutes
at 60.degree. C. and then rinsed with copious amounts of deionized
water and dried under nitrogen. The percent removal of photoresist
and SARC material from the patterned wafer was approximated using
scanning electron microscopy. The results are tabulated in Table 2
hereinbelow.
TABLE-US-00018 TABLE 2 Cleaning results for formulations AK-AQ.
Formulation Percent Cleaning AK 100% AL 100% AM 100% AN 100% AO
100% AP 100% AQ 100%
EXAMPLE 3
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BA-BN for 30 minutes or 60 minutes at 40.degree. C. and
then rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 3 hereinbelow.
TABLE-US-00019 TABLE 3 Cleaning results for formulations BA-BN.
SARC Removal at 30 SARC Removal at 60 Formulation minutes/%
minutes/% BA 5 8 BB 10 97 BC 20 100 BD 50 100 BE 20 95 BF 40 85 BG
50 100 BH 60 100 BI 70 100 BJ 70 100 BK 70 100 BL 85 100 BM 95 100
BN 95 100
EXAMPLE 4
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BO-BT for 30 minutes or 60 minutes at 40.degree. C. and
then rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 4 hereinbelow.
TABLE-US-00020 TABLE 4 Cleaning results for formulations BO-BT.
SARC Removal at 30 SARC Removal at 60 Formulation minutes/%
minutes/% BO 70 80 BP 40 50 BQ 30 40 BR 80 95 BS 90 100 BT 80
95
EXAMPLE 5
Copper etch rates were determined on samples of 1000 Angstrom thick
blanket PVD copper wafers. The samples were dipped in removal
solutions BU-BZ for 60 minutes at 50.degree. C., with or without
stirring (at 60 minutes, 48 hours, and 72 hours), and then rinsed
with copious amounts of deionized water and dried under nitrogen.
The copper etch rate was determined using 4 point probe resistivity
measurements. The results are tabulated in Table 5 hereinbelow.
TABLE-US-00021 TABLE 5 Copper etch rate results for formulations
BU-BZ. Cu etch Cu etch Cu etch rate Cu etch rate rate (with rate
(without (without stirring (without stirring Formu- stirring)/
stirring)/ at 48 hours)/ at 72 hours)/ lation .ANG. min.sup.-1
.ANG. min.sup.-1 .ANG. min.sup.-1 .ANG. min.sup.-1 BU 0.029 0.062
0.081 0.190 BV 0.062 0.007 0.123 0.271 BW 0.022 0.015 0.031 0.116
BX 0.086 0.041 0.335 0.108 BY 0.088 0 0.040 0.115 BZ 0.070 0.138
0.060 0.120
EXAMPLE 6
SARC and crust removal was performed on samples of patterned low-k
dielectric substrate including SARC layers. The samples were dipped
in removal solutions BA.sup.2-BH.sup.2 for 30 minutes at 50.degree.
C., and then rinsed with copious amounts of deionized water and
dried under nitrogen. The percent removal of SARC material and
crust from the patterned wafer was approximated using scanning
electron microscopy. The results are tabulated in Table 6
hereinbelow.
TABLE-US-00022 TABLE 6 Cleaning results for formulations
BA.sup.2-BH.sup.2. Formulation SARC Removal/% Crust Removal/% BAA
98 40 BBB 100 100 BCC 100 100 BDD 98 100 BEE 100 100 BFF 99 100 BGG
100 99 BHH 98 100
EXAMPLE 7
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BI.sup.2-BR.sup.2 for 30 minutes or 60 minutes at
50.degree. C. and then rinsed with copious amounts of deionized
water and dried under nitrogen. The percent removal of SARC
material from the patterned wafer was approximated using scanning
electron microscopy. The results are tabulated in Table 7
hereinbelow.
TABLE-US-00023 TABLE 7 Cleaning results for formulations
BI.sup.2-BR.sup.2. SARC Removal at 30 SARC Removal at 60
Formulation minutes/% minutes/% BII 25 100 BJJ 98 100 BKK 25 100
BLL 99 100 BMM 95 100 BNN 90 100 BOO 40 100 BPP 95 100 BQQ 50 90
BRR 99 100
EXAMPLE 8
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BS.sup.2-BB.sup.3 for 30 minutes at 40.degree. C., and
then rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 8 hereinbelow.
TABLE-US-00024 TABLE 8 Cleaning results for formulations
BS.sup.2-BB.sup.3. Formulation SARC Removal/% BSS 30 BTT 100 BUU
100 BVV 90 BWW 98 BXX 100 BYY 95 BZZ 100 BAAA 70 BBBB 100
EXAMPLE 9
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BC.sup.3-BH.sup.3 for 30 minutes at 40.degree. C., and
then rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 9 hereinbelow.
TABLE-US-00025 TABLE 9 Cleaning results for formulations
BC.sup.3-BH.sup.3. Formulation SARC Removal/% BCCC 10 BDDD 30 BEEE
100 BFFF 95 BGGG 100 BHHH 100
EXAMPLE 10
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BI.sup.3-BM.sup.3 for 30 minutes at 40.degree. C., and
then rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 10 hereinbelow.
TABLE-US-00026 TABLE 10 Cleaning results for formulations
BI.sup.3-BM.sup.3. Formulation SARC Removal/% BIII 5 BJJJ 40 BKKK
100 BLLL 100 BMMM 100
EXAMPLE 11
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BN.sup.3-BS.sup.3 for 30 minutes at 40.degree. C., and
then rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 11 hereinbelow.
TABLE-US-00027 TABLE 11 Cleaning results for formulations
BN.sup.3-BS.sup.3. Formulation SARC Removal/% BNNN 85 BOOO 95 BPPP
60 BQQQ 50 BRRR 30 BSSS 5
EXAMPLE 12
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions BT.sup.3-CE for 30 minutes at 40.degree. C., and then
rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 12 hereinbelow.
TABLE-US-00028 TABLE 12 Cleaning results for formulations
BT.sup.3-CE. Formulation SARC Removal/% BTTT 0 BUUU 50 BVVV 100
BWWW 10 BXXX 20 BYYY 95 BZZZ 0 CA 10 CB 70 CC 0 CD 5 CE 50
EXAMPLE 13
SARC removal was performed on samples of patterned low-k dielectric
substrate including SARC layers. The samples were dipped in removal
solutions CF-CQ for 18 minutes or 30 minutes at 50.degree. C. and
then rinsed with copious amounts of deionized water and dried under
nitrogen. The percent removal of SARC material from the patterned
wafer was approximated using scanning electron microscopy. The
results are tabulated in Table 13 hereinbelow.
TABLE-US-00029 TABLE 13 Cleaning results for formulations CF-CQ.
SARC Removal at 30 SARC Removal at 18 Formulation minutes/%
minutes/% CF 100 100 CG 100 -- CH 100 -- CI 95 40 CJ 100 99 CK 100
100 CL 100 -- CM 100 -- CN 100 -- CO 100 90 CP 100 100 CQ 100
100
EXAMPLE 14
SARC and photoresist removal was performed on samples of patterned
low-k dielectric substrate including SARC and photoresist layers.
The samples were dipped in removal solution CR for 30 minutes at
40.degree. C. and then rinsed with copious amounts of deionized
water and dried under nitrogen. 100% removal of the SARC and
photoresist material from the patterned wafer was observed using
scanning electron microscopy.
EXAMPLE 15
Patterned wafers having post-etch ashless photoresist thereon were
contacted with formulations DA-DH for 20 minutes at 50.degree. C.
Importantly, the wafers included exposed TEOS and low-k dielectric
material. In each case, the photoresist material delaminated from
the surface of the wafer and floated in the formulation and/or the
rinse water container. FESEM micrographs of each wafer indicated
that the photoresist was substantially removed and that the minimum
amount of low-k material attack was observed on the wafers
contacted with formulations DG and DH.
It was determined that the quaternary base and the KOH/KCl were
important components for removing the photoresist from the surface
of the wafer.
EXAMPLE 16
Blanketed silicon nitride (SiN, approximately 300 .ANG. thick),
Black Diamond.TM. (BlackD, approximately 10 k.ANG. thick), and TEOS
wafers (approximately 8000 .ANG. thick) were dipped in removal
formulations DH and DI at 50.degree. C., 60.degree. C., and
70.degree. C. for 20 minutes to determine the etch rate of the
respective materials. Etch rates were determined using a Nanospec.
The etch rates of the respective materials are tabulated below. It
is noted that FTIR of the unprocessed and the processed BlackD
wafer showed that there was no detrimental change in the chemical
structure or the dielectric properties of the BlackD wafer after
processing.
TABLE-US-00030 Formu- Etch rate Etch rate Etch rate lation
Temperature SiN/.ANG. min.sup.-1 BlackD/.ANG. min.sup.-1 TEOS/.ANG.
min.sup.-1 DH 60.degree. C. 0.2 0.6 3.5 70.degree. C. 1.5 0.25 5.7
DI 50.degree. C. 0 0.1 1.35 60.degree. C. 0 0.25 4.30 70.degree. C.
0 0.55 4.25
Patterned wafers having post-etch ashless photoresist thereon were
contacted with formulation DH and DI for 20 minutes at 50.degree.
C., 60.degree. C., and 70.degree. C., rinsed with DI water, and
dried under N.sub.2 gas. Importantly, the wafers included exposed
TEOS and low-k dielectric material. In each case, the photoresist
material delaminated from the surface of the wafer within 1 minute
and did not re-deposit on the surface. FESEM micrographs of each
wafer indicated that the photoresist was substantially removed
therefrom. Processing at 50.degree. C. exhibited the best removal
results with the least amount of damage to the low-k dielectric
material, as evidenced by the FESEM results and the etch rates of
the BlackD and the TEOS.
Accordingly, while the invention has been described herein in
reference to specific aspects, features and illustrative
embodiments of the invention, it will be appreciated that the
utility of the invention is not thus limited, but rather extends to
and encompasses numerous other aspects, features, and embodiments.
Accordingly, the claims hereafter set forth are intended to be
correspondingly broadly construed, as including all such aspects,
features, and embodiments, within their spirit and scope.
* * * * *